Compounded oil



' tion products and the deposition of sludge.

, disadvantages.

,temal combustion engines.

certainof the soaps to these alloy bearings that Patented Nov. 28, 1944 COMPOUNDED OIL Bruce B. Farrington and James 0. Clayton, Berkeley, and Dorr H. Etzler, Albany, Calll'., assignors to Standard Oil Company of California, San Francisco, Calif., a corporation of Delaware No Drawing. Application September 15, 1942, 7 Serial No. 458,450

20 Claims.

This invention relates to the improvement of hydrocarbon oils and the like, in particular; mineral lubricating oils. I This application is a continuation-in-part of our copending application Serial No. 322,946,"filed March 8, 1940, now issued as Patent No. 2,349,817 of May 30, 1944.

Hydrocarbon oils undergo deterioration during use or exposure to the atmosphere. Mere exposure to the air at relatively low temperatures, as in the case of transformer oils and switch oils, results in the gradual formation of acidic oxida- Use of a lubricating oil in the ordinary gasoline engine, as in motor cars, results in a more rapid deterioration of the oil with deposition of sludge and the formation of "varnish on cylinder walls. Use of a lubricating oil in Diesel engines, which operate at higher temperatures and pressures than ordinary gasoline engines, results in even more rapid deterioration with resultant greater The temperatures and pressures involved in Diesel engine operation, around 400- 650 F. and 750-1200 pounds per square inch, cause deposition from ordinary lubricating oils on the moving parts of the engine, such as pistons, piston rings and piston ring slots, of carbonaceous matter of such a cementitious character as to cause sticking of piston rings and greatly to reduce the efficiency of the engine.

It has been found heretofore that some improvement of hydrocarbon oils, especially lubricating oils, can be effected by incorporatingtherein a small amount of a soap of a fatty acid, such as a sodium, calcium or magnesium soap of butyric, capric, palmitic, stearic or oleic acid.

Such soaps, among other things, reduce piston ring sticking in internal combustion engines,

especially Diesel engines-apparently by loosening the cementitious deposits described above, or

by inhibiting the formation of such deposits, or'

both. The action of the added soaps, by virture of the analogy to the common cleansing or detergent action of soaps, came to be known as a detergent action and the soap additives came to be known as detergents.

The use of these soaps or detergents is not, however, without disadvantage. Among other things they are corrosive to certain alloy bearings, such as copper-lead and cadmium-silver alloy bearings, which are-commonly used in in- So' destructive are they can not be used satisfactorily in lubricating oils for internal combustion engines.

It is an object achieved by the present invention to provide a valuable class of additives for lubricating oils, transformer and switch oils, and the like. 7

it is a further object achieved by the present 7 ditives for lubricating oils which are non-cor-' .rosive, or substantially less corrosive than prior soap additives, such as calcium stearate, ltoward alloy bearings.

Other objects achieved by the invention will be apparent from the description and the claims.

We have discovered. that substantial advantages result from incorporating in a hydrocarbon oil or the like, especially a hydrocarbon lubricating oil, a polar substituted metal alkyl carboxylate wherein the polar substituent is of a certain class and is in an alpha, beta or gamma position with respect'to a metal alkylcarboxylate group.

The substltuents that have been found to greatly improve metal alkyl carboxylates as additives for hydrocarbon oils and the like are those containing an element of group VB of the periodic table; that is, containing at least one of the elements nitrogen, phosphorus, arsenic, antimony and bismuth. Preferably, those substituents are employed in which a group VB element is directly connected to the alkyl group of the metal alkyl carboxylate, as in the case of the amino, imino, phosphino, phosphylene and analogous arsenic, antimony and bismuth sub- I -COOM wherein is a metal (or the hydrogen equivalent of a polyvalent meta), the carbon atoms shown attached to C00 are aliphatic carbon atoms, and X is a substituent containing an element of group VB of the periodic table. The unsatisfied carbon valencies shown may be satisfied by hydrogen or hydrocarbon groups (e. g. alkyl groups), by polar groups (including polar groups of the type represented by X, and/or other polar groups), etc.

It will be apparent that three principal constitutional factors may be varied in the additives of this invention: (1) the nature and amount of the substituent X; (2) the nature of the alkyl carboxylic acid which is substituted and whose salt is formed; and (3) the nature of the metal M. These factors are discussed in more detail immediately below.

(l) The substituent X.The following substituents are illustrative:

--N 11 R, Amino =As R Arsylene --N R Imino As Arsenoso N 0 Nitroso As 0 2 Arso NO, Nitro SbR1B-2 Stibino CN Cyano =SbR Stibylene N C Isocyanp Sb 0 Stiboso PRlRi. Phosphmo SbO: Stibo =PR Pbospbylene BiR Rz Bismuthino P 0 Phosphoroso iR Blsmuthylene P O: Phospbo Bi 0 Bismuthoso AsRi R: Arsino Bi 0 1 Bismutho Inthe above, R, R1 and R2 represent hydrogen, hydrocarbon (e. g. alkyl, aryl, aralkyl, and cycloalkyl), or other atoms or groups. More than one of the above or other like substituents may be present in the molecule, and at least one such substituent is present in the alpha, beta or from certain of the hydroxy acids except by replacement ofthe hydroxy group.

Preference is iven to those acids, generally the longer chain alkyl carboxylic acids, whose salts are oil soluble, although the lower acids, even acetic, when properly substituted and used in the form of appropriate metal salts, greatly improve the stability of hydrocarbon oils and inhibit ring sticking and associated phenomena.

gamma position, as indicated, first preference being given to the alpha, position, second to the beta position and third to the gamma position. As stated, other substituents, including polar substituents, may be present in the alkyl chain of the metal alkyl carboxylate, either in the indicated alpha, beta or gamma position or in positions further removed from the metal alkyl carboxylate group.

Those substituents are preferred which do not hydrolyze readily to produce corrosive acids.

However, insofar as certain of the advantages of C10 and higher acids provide adequate oil solubility.

(3) The metal M .-Any mono-or polyvalent metal capable of forming a sufilciently stable salt with the acid chosen may be used. Metals which do not exhibit adverse catalytic activity (such as promoting oxidation) and whose use does not result in excessive wear'are preferred. Examples of metals whose salts may be formed and used in accordance with this invention are lithium, sodium, potassium, calcicum, barium, stron tium, beryllium, magnesium, aluminum, zinc, cadmium, tin, lead, chromium, ,molybdenum, tungsten, manganese, iron, cobalt, nickel, vanadium and bismuth. Basic and mixed, as well as normal simple salts may be employed.

Examples of substituted metal alkyl carboxylates contemplated by this invention are sodium, potassium, calcium, barium, aluminum, magnesium, zinc and nickel alpha, beta and gamma aminobutyrates; the corresponding alpha, beta and gamma amino valerates, caproates, caprates, laurates, myristates, palmitates, stearates, acrylates, crotonates, angelates, oleates, lactates, malonates, succinates, glutarates, adipates, maleates, fumarates, malates, and citrates; also the corresponding im ino, cyano, isocyano, phosphino, phOsphyIena-arsino, arsylene, stibino, stibylene, bismuthino and bismuthylene substituted salts (that is, the salts formed by substituting imino, cyano, etc. for amino).

Itwill be apparent to one skilled in the art that all of 'the' possible substituents X cannot be introduced into each of the positions alpha, beta and gamma of every alkyl carboxylic acid. Thus the presence in an alkyl carboxylic acid of an cycloaliphatic acids and aliphatic acids having an aromatic substituent attached to the alkyl chain (preferably removed by three or more carbon atoms from the alkyl carboxyl group) are comprehended by the invention. In all cases, however, the acid contains at least one carboxyl group attached to one alkyl or aliphatic carbon butyric, capric, lauric, myristic, palmitic, stearic,

etc; also, unsaturated and/or hydroxy and other substituted members of the same series such as oleic, linoleic, linolenic, licanic, lactic and ricinoleic acids. I

alpha, beta or gamma substituent, for example an hydroxyl substituent, may hinder the further substitution of the alpha, beta or gamma position by a certain substituent X of the present invention. In such case, a different substituent X within the scope of the invention, or a different position in the alkyl carboxylic acid, or a different alkyl carboxylic acid may be chosen for substitution; or the hindering alpha, beta or gamma group, such as an hydroxyl group, may be replaced by the desired substituent.

Various methods of forming the metal salts may be employed, one such method being to form an alkali metal salt (as by neutralizing the acid, or saponifying the corresponding ester, with an alkali metal hydroxide) and using the alkali metalsalt per se or converting it into a polyvalent metal salt by adding to an aqueous solution of the-alkali metal salt, a water soluble salt -of a polyvalent metal, thus producing double decomposition and precipitation of the polyvalent metal salt.

The substituted metal alkyl carboxylates of this invention improve hydrocarbon oils in sev- The increase in viscosity of the oil, the neutralization number of the oil at the conclusion of each test, and the amount of naphtha insoluble matter at the conclusion of each test, were also measured. The results of the tests are set forth in Table I below, the additives referred to having been used in theamount of 0.5% by weight based on the oil:

Table I Fresh oil Used 011 cu'Pb smp cd'Ag amp viscosity viscosity New ASTM tran' na htha on Additive in olu- 24 4s 72 24. 4s 72 100 210 100 210 bles hrs. hrs. hrs. hrs. hrs. hrs. F. F. F. F.

3. 9 13.3 37. 4 0. 0 l5. 45. 8 628 57. l 2. 5 44. 0 117. 0 0. 0 17. 0 47. 1 632 57. 0 1, 442 76. 6 4. 97 189 14. 2 67. 2 97. 9 l2. 4 l6. 3 15. 7 630 57. 3 1,148 70. l 4. 49 143 Cs palmitate 47. 3 125. 0 166. 4 9. 5 38. 2 90. 2 632 57. 0 1,361 75. 5 3. 07 221 Ca stearate 84. 4 152. 5 208. l 0. 6 34:8 82. 0 653 57. 5 l, 340 75. 0 4. 02 24K Ca alpha-aminocaprylate +0. 2 3. 9 4. 7 0. 0 0.0 0. 0 685 57. 2 832 62. 8 0. 39 25 Ca t aIpha-hydroxa-aminobutyl. 0 0. 9 l. 4 0. 0 +0. 1 +0. 2 630 57. 1 809 61. 5 0. 48 18 Ca EB IIHfl'OXlXIliflOVBlGl'fltE. +0. 1 0. 0 +0. 3 0.0 0.0 0. 2 630 57. 0 840 62. 5 1. 02 72 Ca cystinate +0. 8 +1. 0 +0. 6 0. 0 +0. 1 +0. 1 635 56. 9 802 61. 4 0. 79 Ca cyanoacctate 2. 0 2. 8 2. i 0. 2 0.2 0. 0 640 57. l 830' 62. 0 0. l3 20 Ca alpha-nitratopropionate. 0. 3 0. 5 1. 0 D. I 0. 3 0. 4 635 57. 3 918 64. l 2. 06 70 Ca beta-nitroprcpionate 1.0 {1. 0 1. 5 0.0 0.0 +0. 2 631 67. 2 1, 111 69. l 3. 61 201 Ba beta-phosphor:atoisobutyrate +0. 4 +0. 8 +0. 5 0. 1 0. 2 0. 3 634 66. 9 844 62. 4 0. 44 26 Ca bcta-phosphatopropionate 0. 6 1. l 1. 4 0.0 0. l 0.0 640 57. 2 1,007 67. 0 0. 19 134 D0 Ba succinamate 0. 2 0.2 0.3 0.0 0. 0 0.0 630 57.0 809 61. 6 2. 85 14 D0 Ca alpha-thiocyanatopropionate 0. 5 0. 7 0. 6 0. 0 0. 0 0. 1 631 57. 0 878 63. 6 3. 05 39 nate, are used. Also, used oil inspections (such as increase in viscosity, increase in neutralization number, and increase in naphtha insoluble matter in the used oil) are benefited by the presence of small amounts of the substituted metal alkyl carboxylates of the invention, or at least are n t at adversely affected as by the commoner soaps and unsubstituted metal alkyl carboxyfatcs, Moreover, the metal alkyl carboxylates of the invention render oils more stable toward oxida tion than the ordinary soaps, and they produce still other advantageous efiects.

The following specific examples will show how a number of properties of hydrocarbon oils are benefited by, and will provide a comparison for judgng the relative utility of, the substituted metal alkyl carboxylates of the invention.

Example I.-A base oil (an SAE blend of 70% Western acid treated naphthenic base oil and 30% Western parafiinic base oil) was tested. with and without the presence of metal alkyl carboxylate additives, to determine its corrosiveness to various alloys of the type used in bearings of internal combustion engines. The Strip corrosion tes was employed in these deterrninations, this test being as follows:

Thin sheets of the indicated bearing metals were cut into strips (copper-lead, 1%" x 1%" x .9,"; cadmium-silver, /2" x 1%" x 1 6), and these strips were immersed in the exemplified oils carried in 2" x 20" glass test tubes; these test 1 tubes were carried in an oil bath maintained at 300 F. :1 F. Each test tube contained approximately. ,300 cc. of oil, and air was bubbled through each tube at the rate of 10 liters per hour. At the end of each of three 24-hour'periods, the strips were removed from the oils,

washed with petroleum ether and carefully wiped with a soft cotton cloth; weight losses of the strips were measured in connection with the weight of each individual strip. The duration of the tests was 72 hours, and the weight losses tabulated below are those found at the end of each 24-hour period.

Example [I -Oil was placed in a beaker in contact with air, maintained at a given temperature. and protected against drafts until darkening due to oxidation had occurred. A sample of the original oil was placed in a glass cell 50 mm. square by 7 mm. thick, and an equal sample of the exposed oil was placed in a second similar glass cell. The glass cells were placed equidistant from an electric light. The light that passed through each glass cell'was caused to impinge on a photoelectric cell. The two photoelectric cells were mounted in two arms of a Wheatstone bridge. The diiference in light transmissions, caused by the different colors of the oils, was thus registered on the Wheatstone bridge. The readings of the bridge were calibrated against the standard ASTM color numbers, and from this the readings of the bridge could be converted into ASTM color numbers (Method Dl55-34T) A base oil (Western paraflinic SAE 30) and the same base oil plus 0.5% by weight of inhibitor were tested, various substituted metal alkyl car- Example IIl.-Calcium cetyl alpha-aminosuc cinate was submitted to various tests in mineral 7 oil, with results as shown in Table III below:

Table III Engine test Bearing corro- Oxygen slon, weight Color absorption, loss in mgms. Stabim cc./100 gms. in 72 hrs. oil in- 1 We Hours to Relative Relative in as causlleg ring flng slot 1 :31:31 g f stic ing c ean iness c e ass 1 2 2 Cu'Pb Cd'Ag hr. hrs. hrs.

Western SAE 30. Nil] 30 Poor Poor 13.9 0.4 6 200 330 390 Do 0.4% Cacetylalpha-aminosuccinate.- 60+ Very good... Very good... D0 0.5% Ca cetylphenate 0.5% Ca 60+ do cetyl alpha-aminosuccinate. Do 1% Ca cetylphenate Do 0.61% Cacctylalpha-aminosuccinate. Do.. 0.5% Ca cetyl phenate 0.5% Ca cetyl alpha-aminosuccinate. Penn. SAE Nil Do 0.5% Ca cetyl phenate Do 0.5% Cacetylalpha-aminosuccinate The various tests indicated in Table III were carried out as follows:

Engine test.-A single cylinder Lauson gasoline spark-ignition engine, 2% inch bore and 2 /2 inch stroke, loaded with an induction generator, was operated under extremely severe conditions, designed to develop fully the tendency of the crankcase lubricant to deteriorate with gum formation and piston ring sticking: oper ation was 0t 1600 revolutions per minute; engine jacket temperature was maintained at 375 F.; crankcase oil temperature was maintained at 220 F.; at periods of 15 hours the operations were interrupted and the condition of the piston rings determined.

Color stability.-The Deep Rock method was used. in which a 50 gram sample of 'oil is held in an open container at 300 F. for six hours and the color increase is determined. Results are given in the units of ASTM Method D155-34T.

Oxygen abs0rption.The Oxidator test described in Industrial and Engineering Chemistry." v01. 28, page 26 (1936) was used. A temperature of 340 F. was used and the results are reported in cubic centimeters of oxygen absorbed per 100 grams of oil.

Co1-rosi0n.The Strip corrosion test in Example I was employed.

The substituted metal alkyl carboxylates of the invention may be advantageously added to any hydrocarbon oil or lubricating oil, such as the more viscous distillates and residues from petroleum oil, viscous olefin polymers, and viscous oils derived from oxides of carbon or other forms of carbon by hydrogenation, and they may be I added with advantage toany of the newer synthetic lubricants, such as amyl naphthalene. The additives of our invention may be used in viscous hydrocarbon oils ranging in viscosity from.

about 60 SSU or lower at 100 F. to 160 SSU or higher at 210 F. The metal alkyl carboxylate may be used, in the finished oil, inamounts ranging from 0.1% or less to 10% or more by weight based on the finished oil, but. preferably it is used in amounts of about 0.1 to usually 0.5 to 2%. Concentrates may be prepared containing more than and up to 50% or'more'of the metal alkyl carboxylate of the invention, alone or together with another additive or other additives, and the concentrate may be diluted with more oil when it is desired to produce the finished oil.

The substituted metal alkyl carboxylates of the invention, as is clear from the examples, are multifunctional in character, and an oil containing one or more of the additives of this invention is improved in several respects. However,

the additives of the invention maybe advantageously combined in hydrocarbon oils with one or more other additives, such as other antioxidants or corrosion inhibitors, other detergents or anti-ring sticking agents, pour point inhibitors, viscosity and viscosity index improvement agents, oiliness, wear, and film strength agents, etc. Specifically, the additives of this invention may be used in mineral or hydrocarbon oils'in combination with any one or more of the following:

(1) Unsubstituted or corrosive carboxylate salts such as the calcium, barium and aluminum salts of-lauric, palmitic, stearic, arachidic, naphthenic, phenyl stearic, benzal stearic, dihydrovabietic, oleic, linoleic and alkylated aromatic acids; also various polar substituted metal carboxylates, such as metal salts of chloro stearic, hydroxy stearic, licanic, cetyl hydroxybenzoic, mercaptostearic, cetyl tartaric, cetyl cystine and dodecyl aminobenzoic acids.

(2) Metal phenates such as the calcium, barium and aluminum salts of cetylphenol, cetyl chlorphenol and cetylthiophenol.

(3) Metal salts of organo substituted oxyand thio-acids of phosphorus, such as calcium cetyl phosphate, aluminum lauryl phosphate and calcium cetylphenyl phosphate.

(4) Carboxylate esters having an alkyl hydroxy substituent (an hydroxy substituent attached to an alkyl carbon atom) near a carbonyl group of the ester, such as the methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, lauryl, dodecyl, tetradecyl, cetyl and octadecyl esters of alpha, beta or gamma hydroxy propionic acid, and the corresponding esters of alpha, beta or gamma hydroxy butyric, valeric, caproic, enanthic,

caprylic, capric, lauric, myristic, palmitlc, stearic, and arachidic acids, as well as the corresponding esters of tartonic, tartaric and citric acids.

The structural formulae and preparation of typical additives capable of use in accordance with this invention are given below:

Calcium alpha-aminocaprylate The structural formula of this substance is as follows:

cmrcmnon-coo I NH: 2 Alpha-amino caprylic acid is prepared by allowing a mixture of equal volumes of enanthaldehyde-ammonia and anhydrous hydrogen cyanide to stand for 18 hours, heating 18 hours with excess 10% hydrochloric acid, evaporating to onethird its volume and precipitating with ammonia. Fifteen grams of alpha-aminocaprylic acid are rated to dryness.

' combined filtrate isevaporated to Calcium alpha-hydroxaminobutyrate The structural formula of this substance is as follows:

(cutout-012L000 Ca NHOH 2 14.2 grams of metallic sodium are dissolved in 200 cc. of absolute alcohol and to the resulting solution a solution of 43 grams of hydroxylamine hydrochloride in 200 cc. of absolute alcohol is added. 21.5 grams of crotonic acid are dissolved in 100 cc. of alcohol and the solution is added to the above solution and the mixture is allowed to stand for three days at room temperature. The alcohol is then evaporated off and the viscous residue is extracted with hot alcohol. The hot alcohol solution is neutralized with a slurry of lime and the solution of calcium salts is evapo- The residue is the desired calcium alpha-hydroxaminobutyrate.

Calcium gamma-oximz'noualerate The structural formula of this substance is as follows:

CHrC-CHz-CHr-COO )Ca NOH 2 Calcium cyano-acetate The structural formula of this substance is as follows:

(NC.CH2COO) zCa 20.5 grams of cyano-acetic acid are dissolved in 500 cc. of water and neutralized with a slurry of lime. The solution is then heated on a steam plate, filtered and evaporated to dryness to recover the calcium cyano-acetate as residue.

Calcium cys tinate The structural formula is:

s-om-onmrmcoo CHCH(NH:)COO} 12.0 grams of cystine and 3.7 grams of calcium hydroxide are added to 500 cc. of water and the mixture is heated on a steam plate for one-half hour and is then filtered. The residue on the filter is leached several times with hot water and the washings combined with the filtrate. The

, dryness to recover the desired salt as residue.

Calcium cetyl alpha-aminosuccinate The structural formula is as follows:

CHr-COOR 5 )CB HnN- H-COO 2 where R represents an organic radical or mixture of radicals derived from an alcohol obtained 7 by saponifying Cosmol" (a hydrogenated sperm oil product). It is probably a mixture of cetyl (CmHsa) and higher alkyl radicals and for convenience is referred to as cetyl.

50 grams of calcium cetyl fumarate and 50 cc. of anhydrous liquid ammonia are warmed to -135- F. in a stainless steel bomb, the pressure reaching 275 pounds per square inch, and the mixture is maintained at this temperature for .9 hours. The bomb is then opened, the contents removed, and ammonia removed by evaporation. The residue constitutes the desired amino salt.

Calcium hydantoate The structural formula is:

(NI-Iz-CO-NH-CI-Iz-COO) 20a 15 grams of glycine are mixed with 12 grams of 'urea and the mixture is heated on a steam plate over night. Excess barium hydroxide solution is then. added to' the mixture and it is heated further until no odor of ammonia is noticeable. The excess urea is thus destroyed and barium hydantoate is formed. The excess barium hydroxide is precipitated with carbon dioxide and the resulting barium carbonate is removed by filtration. A silver nitrate solution is added to the solution of barium hydantoate, causing precipitation of insoluble silver hydantoate. This is filtered oif, washed with cold water and suspended in water. Hydrogen sulfide is passed through the suspended salt causing precipitation of silver sulfide which is then removed by filtration. The filtrate is evaporated to a syrupy consistency and allowed to crystallize. The crystals are filtered, washed and dissolved in waterand neutralized with calcium hydroxide.

Barium beta-phosphonato-z'sobutyrate phinic acid which is recovered in impure form by evaporating the water. It is purified by dissolving in alcohol and precipitating the ammonium salt with ammonia. The salt is washed with alcohol, dissolved in water and filtered. The acid is then obtained by aicidification with HCl followed by evaporation. The solid is extracted with alcohol, filtered, and evaporated to dryness. The purified diacetone phosphinic acid thus produced is oxidized first with nitric acid and then with fuming nitric acid. The excess nitric acid is removed by heating on a water bath. Impure beta-phosphonato-isobutyric acid is formed and it is dissolved in water and barium hydroxide is added until the solution is strongly alkaline.

This solution is heated to boiling and filtered. The barium salt is only slightly soluble in hot water while the impurities dissolve. The filtrate is therefore discarded and the residue remaining on the filter is extracted with cold water, in which the barium salt is soluble, and the extract is evaporated to dryness to recover the purified barium beta-phos-phonato-isobutyrate.

Calcium beta-phosphatopropionate The structural formula of this substance is as follows: I

(PO4(CHZ'CH2'CO0)3)2C9-3 13.6 grams. of beta-iodopropionic acid are dissolved in 200 cc. of water'and 9.5 grams of silver "phosphate are added. The mixture is heated for one-half hour and the silver iodide is filtered oif'. Calcium hydroxide is added until the solution'is neutral and the solution is then evaporated to dryness.

Calcium alpha-nitratopropionate The structural formula of this substance is as follows:

cm on ooo t 20 grams of zinc lactate is added to a mixture of 25 grams of fuming nitric acid and 40 grams of concentrated sulfuric acid, the mixed acid being kept below 40 F. while adding the zinc lactate. The solution is then allowed to warm and most of the excess nitric acid is removed on a hot water bath. The residue is then poured into a large amount of cold water, from which a heavy oil separates. This is neutralized with calcium hydroxide solution and water is removed on a steam plate.

Calcium beta-nitropropionate The structural formula of this substance is as follows: (OzN-CHzCHzCOO) zCa' 15.3 grams of beta iodopropionio acid are dissolved in 400 cc. of water and the solution'is cooled to 40 F. 12.23 grams of silver nitrite are added slowly to the cooled solution and the mixture is allowed .to warm to room temperature. The solution is filtered to remove silver iodide and evaporated to a volume of about 100 cc. under vacuum. Excess calcium hydroxide is added and the excess removed by treating with carbon dioxide and filtering 011 the calcium carbonate The filtered solution is evaporated to dryness.

' Barium succinamate The structural formula is as follows: (muco'onacmoooi 213s 19.8 grams of succinimide are dissolved in water and a solution of 31.6 grams of barium hydroxide octahydrate is added. The solution is evaporated to dryness.

Calcium alpha-thiocyanatopropionate 1 The structural formula isas follows:

CHz-CH-COO i 20 grams of ethyl'alpha-bromopropionate are mixed with an alcoholic solution of 10.7 grams of potassium thiocyanate, The solution is allowed to stand for several days on a steam plate after which potassium bromide is filtered oir. Excess calcium hydroxide solution is then added and the mixture is heated. Carbon dioxide is passed through to remove excess lime. The precipitate of calcium carbonate is removed by filtration and the'filtrate is evaporated to dryness.

The phrase group VB of the periodic table, as used in the specification and claims, refers to that form of the periodic table shown on page 411 of Partington's Chemistry, 4th ed. (1933), MacMillan & Co., London. Thus group VB is the same as the righthand subgroup of group V in the periodic tables shown in the following places: Handbook of Chemistry and Physics, 18th ed., pages 700-701;

the frontispiece of J. Newton Friends A Textbook of Inorganic Chemistry; and vol. I, page 46 of International Critical Tables. Group VB, as used herein, consists of the elements nitrogen, phosphorus, arsenic, antimony and bismuth.

We claim:

1. A composition of matter, comprising a major proportion of a hydrocarbon oil and a small amount, sufficient to stabilize the oil, of an oilsoluble polyvalent metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with. respect to a metal alkyl carboxylate group by a substituent containing an element of group VB of the periodic table, said element being directly connected to the said alkyl carbon atom. i

2. A composition of matter, comprising a major proportion of an oil of lubricating viscosity and a small amount, sufficient to improve properties of the oil affecting its use as a lubricant, of an oil-soluble polyvalent metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent containing an element of group VB of the periodic table, said element being directly connected to the said alkyl carbon atom.

v3. The composition of claim 2, wherein said substituent contains nitrogen.

4. The composition of claim 2, wherein said substituent contains phosphorus.

viscosity and a small amount, sufficient to improve the oil, of a polyvalent metal alkyl carboxylate'substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a phosphino substituent,

including substituted phosphino substituents.

8. A compositon of matter, comprising a, major proportion of a hydrocarbon oil of lubricating viscosity and a small amount, not less than about 0.1% by weight based on finished oil, of a polyvalent metal alkyl carboxylate having in its moleoule the structure C-COOM wherein M is a polyvalent metal, X is a group containing an element of group VB of the peri- Textbook of Inorganic odic table, said element being directly connected to the alkyl group of said metal alkyl carboxylate, and the alkyl carbon atom to which said group X is attached is not more than two carbon atoms removed from the group COOM.

9. The composition of claim 8, wherein said element of group VB is nitrogen.

10. The composition of claim 8, wherein said element of group VB is phosphorus.

11. The composition of claim 8, wherein said metal alkyl carboxylate is an alkaline earth metal alkyl carboxylate.

12. A petroleum lubricating 011 containing dissolved therein about 0.1 to by weight based on finished oil of a polyvalent metal salt of an aliphatic carboxylic acid substituted on an alpha, beta or gamma aliphatic carbon atom with respect to an aliphatic metal carboxylate group by trivalent nitrogen, v

13. A petroleum lubricating 011 containing dissolved therein about 0.1 to 5% by weight based on finished oil of a polyvalent metal. salt of an aliphatic carboxylic acid substituted on an alpha, beta, or gamma aliphatic carbon atom with respect to an aliphatic metal carboxylate group by trivalent phosphorus.

14. A petroleum lubricating oil containing dissolved therein about 0.1 to 5% by weight based on finished oil of a polyvalent metal salt of an aliphatic carboxylic acid substituted on an alpha, beta or gamma aliphatic carbon atom with respect to an aliphatic metal carboxylate group by trivalent arsenic.

15. A composition of matter, comprising a concentrated solution in viscous mineral oil of a metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a subtable.

17. A petroleum lubricating oil containing dissolved therein about 0.1 to 5% by weight based on finished oil of an oil-soluble polyvalent metal salt of a partial ester of succinic acid substituted on an alpha carbon atom of the acid by an amino group.

18. A petroleum lubricating oil containing dissolved therein about 0.1 to 5% by weight based on finished oil of an alkaline earth metal salt of a monoalkyl ester of a higher aliphatic alcohol and alpha amino succinic acid.

19. The oil of claim 18, wherein said salt is the calcium salt of the monocetyl ester of alpha amino succinic acid,

20. A hydrocarbon lubricating oil containing a small amount each, sufllcient to improve the oil as a crankcase lubricant, of an oil-soluble metal salt of an alkylated phenol and an oil-soluble metal salt of an aliphatic carboxylic acid substituted on an alpha, beta or gamma carbon atom with respect to a metal alkyl carboxylate group by a polar substituent containing an element of group VB of the periodic table.

BRUCE B. FARRINGTON. JAMES o. CLAYTON. DORR H. ETZLER. 

